Metallized mesoporous silicate and method of oxidation with the same

ABSTRACT

A metallized mesoporous silicate which is obtained by (i) reacting (a) either a metal peroxide obtained by the reaction of an aqueous hydrogen peroxide solution with at least one metal or metal compound selected from the group consisting of the following 1) to 4) 1) tungsten 2) molybdenum 3) vanadium 4) compounds comprising 4 a ) any of tungsten, molybdenum, and vanadium and 4 b ) at least one element selected from Groups  13  to  16  (excluding oxygen) or a solution of the metal peroxide with (b) a silicon compound in the presence of an alkylamine or a quaternary ammonium salt and separating the resultant silicate; and a process for producing the metallized mesoporous silicate. Also provided is a method of organic synthesis with the silicate.

TECHNICAL FIELD

The present invention provides a novel metallized mesoporous silicatecomprising at least one member selected from tungsten, molybdenum andvanadium, a process for producing the same, and a method of oxidizing anorganic compound using the metallized mesoporous silicate as a catalyst.

BACKGROUND ART

Hydrogen peroxide is a clean and excellent oxidizing agent which isinexpensive, and easily handled, and becomes harmless water afterreaction, and an oxidation reaction using hydrogen peroxide as anoxidizing agent has been highlighted as one of environmentally friendlyproduction processes. In development of an oxidation reaction usinghydrogen peroxide as an oxidizing agent, it is important to develop acatalyst for the oxidation reaction. In particular, from the industrialviewpoint, it has been desired to develop a solid catalyst which isadvantageous to separation and recovery of a catalyst from a reactionsystem. For example, regarding a titanium-containing mesoporous silicatewhich is one of solid catalysts, industrial utilization as anepoxidation catalyst of olefin compounds and as a catalyst forammoximation of ketone compounds has been studied.

On the other hand, a solid catalyst containing a metal other thantitanium and having different catalytic performance and catalyticactivity from a titanium-containing mesoporous silicate has also beendeveloped. For example, regarding a tungsten-containing mesoporoussilicate, as a catalyst for producing cyclohexanediol by reactingcyclohexene and hydrogen peroxide, Applied Catalysis A, 179, 11 (1999),and Chem. Commun., 241 (1998) report a tungsten-containing mesoporoussilicate produced by reacting a tetraalkoxysilane and ammonium tungstateusing cetyl pyridinium bromide as a template in a strongly acidicsolvent. However, such a tungsten-containing mesoporous silicate alonehas low activity and, in order to obtain sufficient activity, aceticacid should be used as a reaction solvent.

For example, regarding a molybdenum-containing mesoporous silicate, as acatalyst for producing phenol by reacting benzene and hydrogen peroxide,Chem. Commun., 979 (1996) reports a molybdenum-containing mesoporoussilicate produced by reacting potassium molybdate and atetraalkoxysilane in a water-ethanol solvent in the presence ofdodecylamine, filtering and washing the reaction product, and calciningthe resulting crystals at 923K.

For example, regarding a vanadium-containing mesoporous silicate, as acatalyst for producing a quinone compound by reacting phenol or naphtholand hydrogen peroxide, J. Chem. Soc., Chem. Commun., 2231 (1995), p.2231, left column, middle paragraph, and J. Chem. Soc., Chem. Commun.,1059 (1994) report a vanadium-containing mesoporous silicate obtained byreacting a solution obtained by adding vanadium sulfate totetraalkoxysilane in a mixed solution of ethanol and isopropanol, withan aqueous solution containing dodecylamine and hydrochloric acid,filtering and washing the resulting crystals, and calcining them. Inaddition, from the results of XRD spectrum measurement, these silicatecompounds are reported to be all MCM-41 type.

Further, regarding an oxidation reaction using hydrogen peroxide as anoxidizing agent, an oxidation reaction for an olefin compound and aBaeyer-Villiger oxidation reaction for a ketone compound are important,and a method using a solid catalyst has also been proposed. For example,a 2-alkoxyalcohol compound is generally produced by a two-stage method,wherein an olefin compound is once oxidized to convert it into anepoxide compound and then the epoxide compound is reacted with analcohol compound. U.S. Pat. No. 6,239,315 proposes a one-stage processfor producing a 2-alkoxyalcohol compound by reacting an olefin compound,hydrogen peroxide and an alcohol compound using two kinds of solidcatalysts having different performances of a titania silicate catalysthaving oxidation catalytic capability and a ZSM-5 catalyst havingalkylation catalytic capability. However, there was a problem that twokinds of the expensive compounds should be used as the catalysts. As amethod without using such two kinds of compounds as catalysts, New. J.Chem., 1998, 797–799 reports a method using a titanium-containing β-typezeolite. However, since a diol is produced as a by-product, selectivityof a 2-alkoxyalcohol is not high and, in order to prevent production ofa diol as a by-product, anhydrous hydrogen peroxide should be used,which is problematic from the viewpoint of prevention of disasters.

Furthermore, as a method for obtaining a lactone compound or an estercompound by subjecting a ketone compound to a Baeyer-Villiger oxidationwith hydrogen peroxide, for example, Nature, 412, 423 (2001), and Chem.Commun., 2190 (2001) report a method using a zeolite-β catalyst carryingtin, and JP 2001-232205 A reports a method using a silica catalystcarrying antimony fluoride. However, these methods use toxic tin andexpensive antimony fluoride, and they can not be necessarily said to beindustrial catalysts.

Moreover, as a method for obtaining an aromatic ester compound by usingan aromatic aldehyde compound, hydrogen peroxide and an alcohol solvent,for example, a method using TS-1 as a catalyst (SynLett, 267 (2002)) anda method of using vanadium oxide and perchloric acid together (OrganicLett., 2, 577 (2000)) are reported. However, in the former, the reactionyield is low and, in the latter, perchloric acid which requires carefulhandling should be used together. Therefore, these catalysts can notnecessarily be said to be industrial catalysts.

DISCLOSURE OF INVENTION

Under these circumstances, in order to develop a novel solid catalystexhibiting catalytic activity in an oxidation reaction, the presentinventor has studied intensively, and have found that a metallizedmesoporous silicate containing at least one member selected fromtungsten, molybdenum and vanadium which is obtained by reacting asilicon compound with a metal oxide obtained by reacting at least onemember selected from tungsten metal, molybdenum metal, vanadium metal,the following tungsten compound, the following molybdenum compound andthe following vanadium compound, which are easily available, with anaqueous hydrogen peroxide solution, in the presence of an alkylamine ora quaternary ammonium salt, exhibits good oxidizing catalytic activityin a reaction between an organic compound and hydrogen peroxide, andfurther exhibits not only oxidizing catalytic activity, but alsocatalytic activity in an alkylation reaction. Thus, the presentinvention has been accomplished.

That is, the present invention provides:

a metallized mesoporous silicate containing at least one member selectedfrom tungsten, molybdenum and vanadium, which is obtained by:

(i) a step of reacting:

(a) a metal peroxide obtained by reacting at least one metal or metalcompound selected from the group consisting of the following 1) to 6)groups with an aqueous hydrogen peroxide solution,

1) tungsten metal, 2) molybdenum metal, 3) vanadium metal,

4) a tungsten compound composed of 4a) tungsten and 4b) at least oneelement selected from the group consisting of Group 13, Group 14, Group15 and Group 16 elements except for oxygen,

5) a molybdenum compound composed of 5a) molybdenum and 5b) at least oneelement selected from the group consisting of Group 13, Group 14, Group15 and Group 16 elements except for oxygen, and

6) a vanadium compound composed of 6a) vanadium and 6b) at least oneelement selected from the group consisting of Group 13, Group 14, Group15 and Group 16 elements except for oxygen, or a solution thereof, with

(b) a silicon compound, in the presence of an alkylamine or a quaternaryammonium salt, and

(ii) a step of separating the resultant reaction product from thereaction mixture (hereinafter abbreviated as the metallized mesoporoussilicate of the present invention); its production process; and furtherthe following production processes which are carried out in the presenceof the metallized mesoporous silicate of the present invention:

a process for producing a diol or β-hydroxyhydroperoxide, whichcomprises reacting hydrogen peroxide and an olefin;

a process for producing a 2-alkoxyalcohol, which comprises reactinghydrogen peroxide, an olefin, and an alcohol;

a process for producing an ester compound, which comprises reactinghydrogen peroxide and a ketone; and

a process for producing an aromatic carboxylic acid ester of an alcohol,which comprises reacting hydrogen peroxide, an aromatic aldehyde and thealcohol.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates an example of a reaction of hydrogen peroxide and anolefin or a carbonyl compound using the metallized mesoporous silicateof the present invention as a catalyst. This exemplifies a process forproducing a diol (2) or β-hydroxyhydroperoxide (3) by reacting hydrogenperoxide and an olefin (1), a process for producing a 2-alkoxy alcohol(4) by reacting hydrogen peroxide, an olefin (1), and an alcohol (5), aprocess for producing an ester compound (7) by reacting hydrogenperoxide and a ketone (6), and a process for producing an aromaticcarboxylic acid ester (10) of an alcohol (9) by reacting hydrogenperoxide, an aromatic aldehyde (8) and the alcohol (9).

EMBODIMENTS FOR CARRYING OUT THE INVENTION

First, the novel metallized mesoporous silicate containing at least onemember selected from the group consisting of tungsten, molybdenum andvanadium of the present invention will be illustrated.

Examples of the tungsten compound include tungsten boride, tungstencarbide, tungsten silicide, tungsten nitride, tungsten phosphide,tungsten sulfide, and the like.

Examples of the molybdenum compound include molybdenum boride,molybdenum carbide, molybdenum silicide, molybdenum nitride, molybdenumphosphide, molybdenum sulfide, and the like.

Examples of the vanadium compound include vanadium boride, vanadiumcarbide, vanadium silicide, vanadium nitride, vanadium phosphide,vanadium sulfide, and the like.

Further, the metals or metal compounds selected from 1) to 6) groups maybe used alone, or two or more of them may be used by mixing.Furthermore, it is preferred to use the metal compound having a smallerparticle size because the metal oxide as the catalyst can be easilyprepared.

Among them, tungsten metal, molybdenum metal, and vanadium metal arepreferably used.

As hydrogen peroxide to be reacted with tungsten metal, molybdenummetal, vanadium metal, the tungsten compound, the molybdenum compound orthe vanadium compound (hereinafter, abbreviated as the metal or metalcompound), an aqueous solution is usually used. Of course, a solution ofhydrogen peroxide in an organic solvent may be used. However, it ispreferred to use an aqueous hydrogen peroxide solution from theviewpoint of easy handling. The concentration of hydrogen peroxide in anaqueous hydrogen peroxide solution or in a solution of hydrogen peroxidein an organic solvent is not particularly limited, but in view of volumeefficacy and safety, the concentration is practically 1 to 60% byweight. As an aqueous hydrogen peroxide solution, a commerciallyavailable aqueous hydrogen peroxide solution is usually used as it is,or if necessary, it may be used by appropriately adjusting theconcentration by dilution or concentration. In addition, as a solutionof hydrogen peroxide in an organic solvent, a solution prepared byextracting an aqueous hydrogen peroxide solution with an organicsolvent, or distilling the solution in the presence of an organicsolvent, may be used.

When the oxide of the metal or metal compound is prepared, the amount ofhydrogen peroxide to be used is usually 3 moles or more, preferably 5moles or more relative to 1 mole of the metal or metal compound, and theupper limit of the amount is not particularly defined.

The reaction of the metal or metal compound with hydrogen peroxide isusually carried out in an aqueous solution. Of course, the reaction maybe carried out in an organic solvent, for example, an ether solvent suchas diethyl ether, methyl tert-butyl ether, tetrahydrofuran, or the like,an ester solvent such as ethyl acetate, and the like, an alcohol solventsuch as methanol, ethanol, tert-butanol, and the like, a nitrile solventsuch as acetonitrile, propionitrile, and the like, or in a mixture ofthe organic solvent and water.

The reaction of the metal or metal compound with hydrogen peroxide isusually carried out by mixing and contacting both of them and, in orderto improve efficacy of contact between the metal or metal compound, andhydrogen peroxide, preferably, the reaction is carried out with stirringso as to sufficiently disperse the metal or metal compound in a solutionfor preparing the oxide of the metal or metal compound. The preparationtemperature of the oxides of the metal and metal compound is usually −10to 100° C.

By reacting the metal or metal compound with hydrogen peroxide in water,in an organic solvent, or in a mixed solvent of water and an organicsolvent, all or a part of the metal or metal compound is dissolved,whereby, a uniform solution or suspension containing the oxide of themetal or metal compound can be prepared. The oxide of the metal or metalcompound may be isolated from the resultant liquid preparation, forexample, by concentration, and may be used as a raw material forpreparing the metallized mesoporous silicate of the present invention,or the liquid preparation may be used as it is as a raw material.

Examples of the silicon compound include a tetraalkoxysilane such astetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, or thelike, and the silicon compound is usually used in such an amount thatsilicon atoms in the tungsten oxide are 4 moles or more relative to 1mole of the tungsten atom.

Examples of the alkylamine include a primary amine substituted with analkyl group having 8 to 20 carbon atoms such as octylamine, nonylamine,decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine,pentadecylamine, heptadecylamine, octadecylamine, nonadecylamine,eicosylamine, and the like; a secondary methylalkylamine having onemethyl group on the substituted primary amine; and the like.

Examples of the quaternary ammonium salt include a hydroxide salt suchas tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,trimethyloctylammonium hydroxide, and the like; a quaternary ammoniumsalt having chlorine or bromine in place of the anion; and the like.

The amount of the alkylamine or quaternary ammonium salt to be used isusually 0.03 to 1 mole relative to 1 mole of the silicon compound.

The reaction of the tungsten oxide with the silicon compound in thepresence of the alkylamine or quaternary ammonium salt is usuallycarried out in the presence of a solvent. Examples of the solventinclude water or an alcohol solvent alone or a mixture of the solventsand, preferably, water, and mixtures of water and the alcohol solventare exemplified. The amount of the solvent to be used is usually 1 to1000 moles relative to 1 mole of the alkylamine or quaternary ammoniumsalt.

The reaction temperature is usually 0 to 200° C.

After completion of the reaction, the product obtained is separated, andthe separated product is washed or calcined to obtain the metallizedmesoporous silicate. For example, a solid produced by the reaction canbe separated, if necessary, after crystallization or filtration.Usually, for example, the reaction mixture is filtered, and theresulting filtration residue was washed with water, followed by dryingto obtain a solid. If necessary, then, the resulting product is washedwith an organic solvent such as methanol, ethanol, and the like toremove the alkylamine or a quaternary ammonium salt, whereby themetallized mesoporous silicate can be obtained. The solid or crystalsobtained by separation can be calcined after drying, or, if necessary,they are calcined after washing with water and drying to obtain thedesired metallized mesoporous silicate.

Calcination is carried out, for example, at 300 to 700° C. in theatmosphere or under an inert atmosphere.

The metallized mesoporous silicate thus obtained has catalyticcapability of an oxidation reaction wherein an organic compound andhydrogen peroxide are reacted to oxidize the organic compound and, atthe same time, catalytic capability of an alkylation reaction.

Hereinafter, various oxidiation reactions using the metallizedmesoporous silicate as a catalyst will be illustrated.

First, the case using an olefin compound will be illustrated. When anolefin compound is used, a diol compound or a β-hydroxyhydroperoxidecompound is obtained. By carrying out such a reaction in the presence ofan alcohol compound, an O-alkylation reaction proceeds together with anoxidation reaction of the olefin compound. Thus, a 2-alkoxyalcoholcompound can also be obtained, as shown in FIG. 1.

The olefin compound is not particularly limited as far as it is anorganic compound having an olefinic carbon-carbon double bond. Examplesthereof include an unsubstituted olefin in which only hydrogen atoms arebound to the double bond (i.e. ethylene), a mono-substituted olefincompound in which one substituent and three hydrogen atoms are bound tothe double bond, a di-substituted olefin compound in which twosubstituents and two hydrogen atoms are bound to the double bond, atri-substituted olefin compound in which three substituents and onehydrogen atom are bound to the double bond, and a tetra-substitutedolefin compound in which four substituents are bound to the double bond.The substituents (R₁ and R₃, or R₂ and R₄ in the compound of the formula(1) in FIG. 1) bound to a carbon-carbon double bond may be takentogether to form a part of a ring structure.

Examples of the substituent (R₁ to R₄ in the compounds of the formulas(1) to (6) in FIG. 1) include a substituted or unsubstituted alkylgroup, a substituted or unsubstituted alkoxy group, a substituted orunsubstituted aryl group, a substituted or unsubstituted aryloxy group,a substituted or unsubstituted aralkyl group, a substituted orunsubstituted aralkyloxy group, a halogen atom, a substituted orunsubstituted alkylcarbonyl group, a substituted or unsubstitutedarylcarbonyl group, a substituted or unsubstituted aralkylcarbonylgroup, a substituted or unsubstituted alkoxycarbonyl group, asubstituted or unsubstituted aryloxycarbonyl group, a substituted orunsubstituted aralkyloxycarbonyl group, a carboxyl group, and the like.

Examples of the unsubstituted alkyl group include a straight, branchedor cyclic unsubstituted alkyl group having 1 to 20 carbon atoms such asa methyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-nonyl group, an-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group,a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, an-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, an-eicosyl group, a cyclopentyl group, a cyclohexyl group, a menthylgroup, and the like. Examples of the substituted alkyl group include analkyl group substituted with the following alkoxy group, aryloxy group,aralkyloxy group, halogen atom, alkylcarbonyl group, arylcarbonyl group,aralkylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group,aralkyloxycarbonyl group, carboxyl group, or the like. Examples of thespecific substituted alkyl group include a chloromethyl group, afluoromethyl group, a trifluoromethyl group, a methoxymethyl group, anethoxymethyl group, a methoxyethyl group, a carbomethoxymethyl group,and the like.

Examples of the unsubstituted alkoxy group include an unsubstitutedalkoxy group composed of the above unsubstituted alkyl group and anoxygen atom, for example, a straight, branched or cyclic alkoxy grouphaving 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxygroup, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, an-hexyloxy group, a n-heptyloxy group, a n-nonyloxy group, a n-decyloxygroup, an undecyloxy group, a n-dodecyloxy group, a n-tridecyloxy group,a n-tetradecyloxy group, a n-pentadecyloxy group, a n-hexadecyloxygroup, a n-heptadecyloxy group, a n-octadecyloxy group, a n-nonadecyloxygroup, a n-eicosyloxy group, a cyclopentyloxy group, a cyclohexyloxygroup, a menthyloxy group, or the like. Examples of the substitutedalkoxy group include, an alkoxy group having a substituent such as ahalogen atom, an alkoxy group, or the like as in the substituted alkylgroup above. Examples of the specific substituted alkoxy group include achloromethoxy group, a fluoromethoxy group, a trifluoromethoxy group, amethoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, andthe like.

Examples of the unsubstituted aryl group include, for example, a phenylgroup, a naphthyl group, and the like. Examples of the substituted arylgroup include an aryl group substituted with a substituent such as theabove alkyl, aryl, or alkoxy group, as well as with the followingaralkyl group such as a benzyl group, aryloxy group, aralkyloxy group,halogen atom, or the like. Examples of the specific substituted arylgroup include a 2-methylphenyl group, a 4-chlorophenyl group, a4-methylphenyl group, a 4-methoxyphenyl group, a 3-phenoxyphenyl group,and the like.

Examples of the substituted or unsubstituted aryloxy group include anaryloxy group composed of the above substituted or unsubstituted arylgroup and an oxygen atom. Specific examples thereof include, forexample, a phenoxy group, a 2-methylphenoxy group, a 4-chlorophenoxygroup, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a3-phenoxyphenoxy group, and the like.

Examples of the unsubstituted or substituted aralkyl group include anaralkyl group composed of the above unsubstituted or substituted arylgroup and the above unsubstituted or substituted alkyl group. Specificexamples thereof include, for example, a benzyl group, a 4-chlorobenzylgroup, a 4-methylbenzyl group, a 4-methoxybenzyl group, a3-phenoxybenzyl group, a 2,3,5,6-tetrafluorobenzyl group, a2,3,5,6-tetrafluoro-4-methylbenzyl group, a2,3,5,6-tetrafluoro-4-methoxybenzyl group, a2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group, and the like.

Examples of the substituted or unsubstituted aralkyloxy group include anaralkyloxy group composed of the above substituted or unsubstitutedaralkyl group and an oxygen atom. Specific examples thereof include, forexample, a benzyloxy group, a 4-chlorobenzyloxy group, a4-methylbenzyloxy group, a 4-mehoxybenzyloxy group, a 3-phenoxybenzyloxygroup, a 2,3,5,6-tetrafluorobenzyloxy group, a2,3,5,6-tetrafluoro-4-methylbenzyloxy group, a2,3,5,6-tetrafluoro-4-methoxybenzyloxy group, a2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, abromine atom, and the like.

Examples of the substituted or unsubstituted alkylcarbonyl group,substituted or unsubstituted arylcarbonyl group, and substituted orunsubstituted aralkylcarbonyl group include groups composed of acarbonyl group and the above substituted or unsubstituted alkyl group,substituted or unsubstituted aryl group or substituted or unsubstitutedaralkyl group. Specific examples thereof include, for example, amethylcarbonyl group, an ethylcarbonyl group, a phenylcarbonyl group, abenzylcarbonyl group, and the like.

Examples of the substituted or unsubstituted alkoxycarbonyl group,substituted or unsubstituted aryloxycarbonyl group and substituted orunsubstituted aralkyloxycarbonyl group include groups composed of acarbonyl group and the above substituted or unsubstituted alkoxy group,substituted or unsubstituted aryloxy group, or aralkyloxy group,respectively. Specific examples thereof include, for example, amethoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group,a benzyloxycarbonyl group, and the like.

Examples of the olefin compound include 1-hexene, 1-heptene, 1-octene,1-dodecene, styrene, 4-methylstyrene, 1,7-octadiene, allylbenzene,allylanisole, allyl chloride, allyl ethyl ether, allyl benzyl ether,isobutene, 2-methyl-1-pentene, 2,4,4-trimethyl-1-pentene,2-ethyl-1-butene, α-methylstyrene, α-phenylstyrene,methylenecyclobutane, methylenecyclopentane, methylenecyclohexane,β-pinene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene,3,5-dimethylcyclopentene, 3,4,5-trimethylcyclopentene,3-chlorocyclopentene, 3-methylcyclohexene, 4-methylcyclohexene,3,4-dimethylcyclohexene, 3,5-dimethylcyclohexene,3,4,5-trimethylcyclohexene, 2-hexene, 3-hexene, 5-dodecene, norbornene,phenanthrene, 1,2,3,6-tetrahydrophthalic acid anhydride,dicyclopentadiene, indene, methyl3,3-dimethyl-2-(1-propenyl)cyclopropanecarboxylate, ethyl3,3-dimethyl-2-(1-propenyl)cyclopropanecarboxylate, 2-methyl-2-pentene,3-methyl-2-pentene, 3-ethyl-2-pentene, 2-methyl-2-hexene,3-methyl-2-hexene, 2-methyl-1-phenylpropene, 2-phenyl-2-butene,1-methylcyclopentene, 1,3-dimethylcyclopentene,1,4-dimethylcyclopentene, 1,5-dimethylcyclopentene,1,3,5-trimethylcyclopentene, 1,3,4-trimethylcyclopentene,1,4,5-trimethylcyclopentene, 1,3,4,5-tetramethylcyclopentene,1-methylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene,1,5-dimethylcyclohexene, 1,3,5-trimethylcyclohexene,1,3,4-trimethylcyclohexene, 1,4,5-trimethylcyclohexene,1,3,4,5-tetramethylcyclohexene, isophorone, 2-carene, 3-carene,α-pinene, methyl3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, ethyl3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, isopropyl3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, tert-butyl3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, cyclohexyl3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, menthyl3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate, benzyl3,3-diemthyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,(4-chlorobenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,(3-phenoxybenzyl)3,3-diemthyl-2-(2-methyl-1-propenyl)cyclopropanecarboxylate,2,3-dimethyl-2-butene, 1,2-dimethylcyclopentene,1,2-dimethylcyclohexene, 1,2,3,4,5,6,7,8-octahydronaphthalene,1-isopropylidene-2-carboethoxy-3-methylcyclopropane,cyclohexylidenecyclohexane, tetraphenylethylene,2,3-dimethyl-4-methoxyindene, 2,3-di(4-acetoxyphenyl)-2-butene, and thelike.

Among these olefin compounds, there are compounds having asymmetriccarbons in the molecules thereof and having optical isomers. In thepresent invention, optical isomers alone or a mixture thereof may beused.

The amount of the metallized mesoporous silicate catalyst to be used inthe reaction of an olefin compound and hydrogen peroxide may be acatalytic amount relative to the olefin compound and is usually 0.001part by weight or more relative to 1 part by weight of the olefincompound. The upper limit is not particularly defined but, from theeconomical viewpoint, the amount is practically 1 part by weight or lessrelative to 1 part by weight of the olefin compound.

Hydrogen peroxide is usually used as an aqueous solution. Of course, asolution of hydrogen peroxide in an organic solvent may be used. Theconcentration of hydrogen peroxide in an aqueous hydrogen peroxidesolution or in a solution in an organic solvent is not particularlylimited, but in view of volume efficacy and safety, the concentration ispractically 1 to 60% by weight. As an aqueous hydrogen peroxidesolution, usually, a commercially available aqueous hydrogen peroxidesolution may be used as it is, or if necessary, by adjusting theconcentration of hydrogen peroxide thereof by dilution, concentration,and the like. As a solution of hydrogen peroxide in an organic solvent,for example, a solution prepared by means of extraction of an aqueoushydrogen peroxide solution with an organic solvent, distillation of anaqueous hydrogen peroxide solution in the presence of an organicsolvent, and the like, may be used.

The amount of hydrogen peroxide to be used for the reaction with anolefin compound is usually 1 mole or more relative to 1 mole of theolefin compound. The upper limit of the amount is not particularlydefined, but the amount is practically 10 moles or less relative to 1mole of the olefin compound from the economical viewpoint.

The reaction of the olefin compound and hydrogen peroxide is usuallycarried out in water or an organic solvent. Examples of the organicsolvent include an ether solvent such as diethyl ether, methyltert-butyl ether, tetrahydrofuran, or the like, an ester solvent such asethyl acetate, or the like, a tertiary alcohol solvent such astert-butanol, or the like, a nitrile solvent such as acetonitrile,propionitrile, or the like, etc. The amount of water or the organicsolvent to be used is not particularly limited, but in view of volumeefficacy, the amount is practically 100 parts by weight or less relativeto 1 part by weight of the olefin compound.

By reacting an olefin compound and hydrogen peroxide in the presence ofthe metallized mesoporous silicate catalyst of the present invention, aβ-hydroxyhydroperoxide compound and a diol compound are obtained. Sincea production ratio is different depending on the structure of an olefincompound and reaction conditions, reaction conditions may beappropriately selected according to a particular purpose. In addition,an oxygen-containing organic compound other than aβ-hydroxyhydroperoxide compound and a diol compound may be produced as aby-product.

For example, when the reaction is carried out in an organic solvent, theβ-hydroxyhydroperoxide compound is apt to be easily obtained as a mainproduct. In addition, since as a water content in a reaction system issmaller, a β-hydroxyhydroperoxide compound is apt to be easily obtained,for selective production of β-hydroxyhydroperoxide compound, it ispreferred to carry out the reaction under conditions of a reducedcontent of water in a reaction system, for example, in the presence of adehydrating agent in a reaction system. Examples of the dehydratingagent include anhydrous magnesium sulfate, anhydrous sodium sulfate,boric anhydride, polyphosphoric acid, diphosphorus pentaoxide, and thelike. The amount to be used may be appropriately determined depending onthe amount of water present in the reaction system.

When the reaction temperature is too low, the oxidation reaction hardlyproceeds and, when the reaction temperature is too high, a side reactionsuch as polymerization of a starting olefin compound is liable toproceed. Therefore, the practical reaction temperature is in a range of0 to 200° C. When the reaction temperature is low, aβ-hydroxyhydroperoxide compound is apt to be easily produced and, as thereaction temperature rises higher, a diol compound is apt to be easilyproduced.

The reaction of an olefin compound and hydrogen peroxide is usuallycarried out by contacting and mixing the olefin compound, hydrogenperoxide and the metallized mesoporous silicate catalyst, and the orderof mixing is not particularly limited. The reaction may be carried outunder ordinary pressure conditions, or may be carried out underpressurized conditions. The progress of the reaction can be confirmed bya conventional analytical means such as gas chromatography, highperformance liquid chromatography, thin layer chromatography, nuclearmagnetic resonance spectrum analysis (hereinafter, abbreviated as NMR),infrared absorption spectrum analysis (hereinafter, abbreviated as IR),and the like.

After completion of the reaction, an oxygen-containing organic compoundthus produced can be separated and isolated by subjecting the reactionmixture as it is or, if necessary, after degrading remaining hydrogenperoxide with a reducing agent such as sodium sulfite and filtering offthe metallized mesoporous silicate catalyst, to concentration,crystallization, and the like. Further, an oxygen-containing organiccompound can be separated and isolated by, if necessary, addition ofwater and/or a water-insoluble organic solvent to the reaction mixture,followed by extraction and concentration of the resulting organic layer.The oxygen-containing organic compound thus isolated may be furtherpurified by means of distillation, column chromatography, and the like.

Examples of the water-insoluble organic solvent include an aromatichydrocarbon solvent such as toluene, xylene, and the like, a halogenatedhydrocarbon solvent such as dichloromethane, chloroform, chlorobenzene,and the like, an ether solvent such as diethyl ether, methyl tert-butylether, tetrahydrofuran, and the like, an ester solvent such as ethylacetate, and the like, etc. Its amount to be used is not particularlylimited.

The metallized mesoporous silicate catalyst or a solution containing themetallized mesoporous silicate catalyst separated from the reactionmixture by filtration, liquid phase separation, and the like can bere-used as a catalyst in the reaction of an olefin compound and hydrogenoxide as it is or, if necessary, after concentration, and the like.

Examples of the β-hydroxyhydroperoxide compound thus obtained (thecompound of the formula (3) in FIG. 1) include1-hydroxy-2-hydroperoxyhexane, 2-hydroxy-1-hydroperoxyhexane,1-hydroxy-2-hydroperoxyheptane, 2-hydroxy-1-hydroperoxyheptane,1-hydroxy-2-hydroperoxyoctane, 2-hydroxy-1-hydroperoxyoctane,1-hydroxy-2-hydroperoxydodecane, 2-hydroxy-1-hydroperoxydodecane,1-hydroxy-2-phenyl-2-hydroperoxyethane,1-hydroxy-2-(4-methylphenyl)-2-hydroperoxyethane,1-hydroxy-2-hydroperoxy-3-phenylpropane,2-hydroxy-l-hydroperoxy-3-phenylpropane,1-hydroxy-2-hydroperoxy-3-(4-methoxyphenyl)propane,2-hydroxy-1-hydroperoxy-3-(4-methoxyphenyl)propane,1-hydroxy-2-hydroperoxy-3-chloropropane,2-hydroxy-1-hydroperoxy-3-chloropropane,1-hydroxy-2-hydroperoxy-3-ethoxypropane,2-hydroxy-1-hydroperoxy-3-ethoxypropane, (3-hydroxy-2-hydroperoxypropy)benzyl ether, (2-hydroxy-3-hydroperoxyethyl)benzyl ether, methyl3,3-dimethyl-2-(1-hydroxy-2-hydroperoxyethyl)cyclopropanecarboxylate,methyl3,3-dimethyl-2-(2-hydroxy-1-hydroperoxyethyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(1-hydroxy-2-hydroperoxyethyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(2-hydroxy-1-hydroperoxyethyl)cyclopropanecarboxylate,2-hydroperoxy-2-methyl-1-propanol,2,4,4-trimethyl-2-hydroperoxy-1-pentanol,2-ethyl-2-hydroperoxy-1-butanol, 2-methyl-2-hydroperoxy-1-pentanol,2-hydroperoxy-2-phenyl-1-propanol, 2,2-diphenyl-2-hydroperoxyethanol,1-hydroperoxy-1-(hydroxymethyl)cyclobutane,1-hydroperoxy-1-(hydroxymethyl)cyclopentane,1-hydroperoxy-1-(hydroxymethyl)cyclohexane,bicyclo[3.1.1]-2-hydroperoxy-2-(hydroxymethyl)-6,6-dimethylheptane,1-hydroperoxy-2-hydroxycyclopentane, 1-hydroperoxy-2-hydroxycyclohexane,1-hydroperoxy-2-hydroxycycloheptane, 1-hydroperoxy-2-hydroxycyclooctane,1-hydroperoxy-2-hydroxy-3-methylcyclopentane,1-hydroperoxy-2-hydroxy-4-methylcyclopentane,1-hydroperoxy-2-hydroxy-3,4-dimethylcyclohexane,1-hydroperoxy-2-hydroxy-3,4,5-trimethylcyclohexane,2-hydroperoxy-3-hydroxyhexane, 3-hydroperoxy-2-hydroxyhexane,bicyclo[2.2.1]heptane-2-hydroperoxy-3-ol, methyl3,3-dimethyl-2-(1-hydroxy-2-hydroperoxypropyl)cyclopropanecarboxylate,methyl3,3-dimethyl-2-(2-hydroxy-1-hydroperoxypropyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(1-hydroxy-2-hydroperoxypropyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(2-hydroxy-1-hydroperoxypropyl)cyclopropanecarboxylate,2-methyl-2-hydroperoxy-3-hydroxypentane,3-methyl-3-hydroperoxy-2-hydroxyhexane,1-methyl-1-hydroperoxy-2-hydroxycyclopentane,1,3-dimethyl-1-hydroperoxy-2-hydroxycyclohexane,1,3,5-trimethyl-1-hydroperoxy-2-hydroxycyclohexane,3-hydroperoxy-4-hydroxycarene, methyl3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,isopropyl3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,tert-butyl3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,cyclohexyl3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,menthyl3,3-dimethyl-2-(2-methyl-2-hydroxyperoxy-1-hydroxypropyl)cyclopropanecarboxylate,benzyl3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,(4-chlorobenzyl)3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,(3-phenoxybenzyl)3,3-dimethyl-2-(2-methyl-2-hydroperoxy-1-hydroxypropyl)cyclopropanecarboxylate,2,3-dimethyl-2-hydroperoxy-3-hydroxybutane,1,2-dimethyl-1-hydroperoxy-2-hydroxycyclopentane,1,2-dimethyl-1-hydroperoxy-2-hydroxycyclohexane,bicyclo[4.4.0]-1-hydroperoxy-6-hydroxydecane,1-hydroxyperoxy-1-(1-hydroxy-1-methylethyl)-2,3-dimethylcyclopentane,1-hydroxy-1-(1-hydroperoxy-1-methylethyl)-2,3-dimethylcyclopentane,1-hydroperoxy-1-(1-hydroxycyclohexyl)cyclohexane,1-hydroperoxy-1-hydroxy-1,1,2,2-tetraphenylethane,2-hydroperoxy-3-hydroxy-2,3-dimethyl-4-methoxyindane,2-hydroxy-3-hydroperoxy-2,3-dimethyl-4-methoxyindane,2,3-di(4-acetoxyphenyl)-2-hydroperoxy-3-hydroxybutane, and the like.

Examples of the diol compound (the compound of the formula (2) inFIG. 1) include 1,2-hexanediol, 1,2-haptanediol, 1,2-octanediol,1,2-dodecanediol, phenylethylene glycol, (4-methylphenyl)ethyleneglycol, 3-phenyl-1,2-propanediol, 3-(4-methoxyphenyl)-1,2-propanediol,3-chloro-1,2-propanediol, 3-ethoxy-1,2-propanediol,3-benzyloxy-1,2-propanediol, methyl3,3-dimethyl-2-(1,2-dihydroxyethyl)cyclopropanecarboxylate,1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,2-cycloheptanediol,1,2-cyclooctanediol, 3-methyl-1,2-cyclopentanediol,4-methyl-1,2-cyclopentanediol, 3,4-dimethyl-1,2-cyclohexanediol,3,4,5-trimethyl-1,2-cyclohexanediol, 2,3-hexanediol,bicyclo[2.2.1]heptane-2,3-diol, methyl3,3-dimethyl-2-(1,2-dihydroxypropyl)cyclopropanecarboxylate, ethyl3,3-dimethyl-2-(1,2-dihydroxypropyl)cyclopropanecarboxylate,2-methyl-1,2-propanediol, 2-methyl-1,2-pentanediol,2,4,4-trimethyl-1,2-pentanediol, 2-ethyl-1,2-butanediol,2-phenyl-1,2-propanediol, 1,1-diphenyl-1,2-ethanediol,1-(hydroxymethyl)cyclobutanol, 1-(hydroxymethyl)cyclopentanol,1-(hydroxymethyl)cyclohexanol,bicyclo[4.1.1]-2-hydroxymethyl-6,6-dimethylheptane-2-ol,2-methyl-2,3-pentanediol, 3-methyl-2,3-hexanediol,1-methyl-1,2-cyclopentanediol, 1-methyl-1,2-cyclohexanediol,1,3-dimethyl-1,2-cyclohexanediol, 1,3,5-trimethyl-1,2-cyclohexanediol,3,4-carenediol, methyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,isopropyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,tert-butyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,cyclohexyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,menthyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,benzyl3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,(4-chlorobenzyl)3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,(3-phenoxybenzyl)3,3-dimethyl-2-(2-methyl-1,2-dihydroxypropyl)cyclopropanecarboxylate,pinacol, 1,2-dimethyl-1,2-cyclopentanediol,1,2-dimethyl-1,2-cyclohexanediol,1,2-di(4-acetoxyphenyl)-1,2-butanediol, bicyclo[4.4.0]decane-1,6-diol,1,1,2,2-tetraphenylethylene glycol,2,3-dihydroxy-2,3-dimethyl-4-methoxyindane, and the like.

When an optically active substance is used as an olefin compound, anoptically active oxygen-containing organic compound is obtainedaccording to a position of an asymmetric carbon.

By carrying out the above reaction of the olefin compound and hydrogenperoxide in the presence of a primary alcohol compound or a secondaryalcohol compound (hereinafter, abbreviated as an alcohol compound), anO-alkylation reaction proceeds together with the oxidation reaction ofthe olefin compound, whereby, a 2-alkoxyalcohol compound is obtained.

Examples of the alcohol compound (the compound represented by theformula (5): R₅OH in FIG. 1) include a primary alcohol compound or asecondary alcohol compound having 1 to 4 carbon atoms such as methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and the like.

The amount of the alcohol compound to be used is usually 1 mole or morerelative to 1 mole of the olefin compound to be used, and an upper limitis not particularly defined. For example, the alcohol compound may beused in large excess relative to the olefin compound so as to also serveas a reaction solvent.

The reaction temperature is usually 0 to 200° C. and, as a reactiontemperature rises higher, a 2-alkoxyalcohol compound is apt to be easilyproduced.

Examples of the 2-alkoxyalcohol compound (the compound represented bythe formula (4) in FIG. 1) include 1-hydroxy-2-methoxyhexane,2-hydroxy-1-methoxyhexane, 1-hydroxy-2-ethoxyheptane,2-hydroxy-1-ethoxyheptane, 1-hydroxy-2-propoxyoctane,2-hydroxy-1-propoxyoctane, 1-hydroxy-2-methoxydodecane,2-hydroxy-1-methoxydodecane, 1-hydroxy-2-phenyl-2-ethoxyethane,1-hydroxy-2-(4-methylphenyl)-2-ethoxyethane,1-hydroxy-2-methoxy-3-phenylpropane,2-hydroxy-1-methoxy-3-phenylpropane,1-hydroxy-2-ethoxy-3-(4-methoxyphenyl)propane,2-hydroxy-1-ethoxy-3-(4-methoxyphenyl)propane,1-hydroxy-2-propoxy-3-chloropropane,2-hydroxy-1-propoxy-3-chloropropane,1-hydroxy-2-methoxy-3-ethoxypropane,2-hydroxy-l-methoxy-3-ethoxypropane, (3-hydroxy-2-ethoxypropyl) benzylether, (2-hydroxy-3-ethoxyethyl) benzyl ether,2-methoxy-2-methyl-1-propanol, 2,4,4-trimethyl-2-methoxy-1-pentanol,2-ethyl-2-ethoxy-1-butanol, 2-methyl-2-propoxy-1-pentanol,2-methoxy-2-phenyl-1-propanol, 2,2-diphenyl-2-butoxyethanol,1-methoxy-1-(hydroxymethyl)cyclobutane,1-ethoxy-1-(hydroxymethyl)cyclopentane,1-methoxy-1-(hydroxymethyl)cyclohexane,bicyclo[3.1.1]-2-ethoxy-2-(hydroxymethyl)-6,6-dimethylheptane,1-methoxy-2-hydroxycyclopentane, 1-ethoxy-2-hydroxycyclohexane,1-propoxy-2-hydroxycycloheptane, 1-butoxy-2-hydroxycyclooctane,1-methoxy-2-hydroxy-3-methylcyclopentane,1-ethoxy-2-hydroxy-4-methylcyclopentane,1-propoxy-2-hydroxy-3,4-dimethylcyclohexane,1-butoxy-2-hydroxy-3,4,5-trimethylcyclohexane,2-methoxy-3-hydroxyhexane, 3-ethoxy-2-hydroxyhexane,bicyclo[2.2.1]heptane-2-propoxy-3-ol, methyl3,3-dimethyl-2-(1-hydroxy-2-ethoxypropyl)cyclopropanecarboxylate, methyl3,3-dimethyl-2-(2-hydroxy-1-methoxypropyl)cyclopropanecarboxylate, ethyl3,3-diemthyl-2-(1-hydroxy-2-methoxypropyl)cyclopropanecarboxylate, ethyl3,3-dimethyl-2-(2-hydroxy-1-butoxypropyl)cyclopropanecarboxylate,2-methyl-2-methoxy-3-hydroxypentane, 3-methyl-3-ethoxy-2-hydroxyhexane,1-methyl-1-propoxy-2-hydroxycyclopentane,1,3-dimethyl-1-butoxy-2-hydroxycyclohexane,1,3,5-trimethyl-1-methoxy-2-hydroxycyclohexane,3-ethoxy-4-hydroxycarene, methyl3,3-dimethyl-2-(2-methyl-2-methoxy-1-hydroxypropyl)cyclopropanecarboxylate,ethyl3,3-dimethyl-2-(2-methyl-2-ethoxy-2-hydroxypropyl)cyclopropanecarboxylate,isopropyl3,3-dimethyl-2-(2-methyl-2-propoxy-1-hydroxypropyl)cyclopropanecarboxylate,tert-butyl3,3-dimethyl-2-(2-methyl-2-butoxy-1-hydroxypropyl)cyclopropanecarboxylate,cyclohexyl3,3-dimethyl-2-(2-methyl-2-methoxy-1-hydroxypropyl)cyclopropanecarboxylate,menthyl3,3-dimethyl-2-(2-methyl-2-methoxy-1-hydroxypropyl)cyclopropanecarboxylate,benzyl3,3-dimethyl-2-(2-methyl-2-ethoxy-1-hydroxypropyl)cyclopropanecarboxylate,(4-chlorobenzyl)3,3-diemthyl-2-(2-methyl-2-ethoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluorobenzyl)3,3-dimethyl-2-(2-methyl-2-propoxyl-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methylbenzyl)3,3-dimethyl-2-(2-methyl-2-propoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxybenzyl)3,3-dimethyl-2-(2-methyl-2-butoxy-1-hydroxypropyl)cyclopropanecarboxylate,(2,3,5,6-tetrafluoro-4-methoxymethylbenzyl)3,3-dimethyl-2-(2-methyl-2-butoxy-1-hydroxypropyl)cyclopropanecarboxylate,(3-phenoxybenzyl)3,3-dimethyl-2-(2-methyl-2-methoxy-1-hydroxypropyl)cyclopropanecarboxylate,2,3-dimethyl-2-methoxy-3-hydroxybutane,1,2-dimethyl-1-hydroperoxy-2-ethoxycyclopentane,1,2-dimethyl-1-ethoxy-2-hydroxycyclohexane,bicyclo[4.4.0]-1-propoxy-6-hydroxydecane,1-propoxy-1-(1-hydroxy-1-methylethyl)-2,3-dimethylcyclopentane,1-hydroxy-1-(1-methoxy-1-methylethyl)-2,3-dimethylcyclopentane,1-methoxy-1-(1-hydroxycyclohexyl)cyclohexane,1-ethoxy-1-hydroxy-1,1,2,2-tetraphenylethane,2-propoxy-3-hydroxy-2,3-dimethyl-4-methoxyindane,2-hydroxy-3-butoxy-2,3-dimethyl-4-methoxyindane,2,3-di(4-acetoxyphenyl)-2-methoxy-3-hydroxybutane, and the like.

Then, a reaction using a ketone compound will be illustrated. When aketone compound is used, a Baeyer-Villiger reaction product is obtained.As shown in FIG. 1, for example, when a cyclic ketone compound is usedas the ketone compound, a lactone compound is obtained.

Examples of the ring structure of the cyclic ketone compound include acyclobutane ring, a cyclopentane ring, a cyclohexane ring, acycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecanering, a cyclododecane ring, a benzene ring, and the like, and such aring may be substituted with an alkyl group, an alkoxy group, an arylgroup, a halogen atom, or the like.

Examples of the substituent represented by R₁ or R₂ include the groupsas described above. Examples of the alkyl group include a straight,branched or cyclic alkyl group such as a methyl group, an ethyl group, an-propyl group, an isopropyl group, a n-butyl group, an isobutyl group,a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexylgroup, a n-octyl group, an isooctyl group, a n-nonyl group, a n-decylgroup, a cyclopentyl group, a cyclohexyl group, and the like. The alkylgroup may have a substituent, and examples of the substituent include analkoxy group such as a methoxy group, an ethoxy group, a n-propxy group,an isopropoxy group, a n-butoxy group, and the like, and a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom, and the like.Examples of the alkyl group having the substituent include achloromethyl group, a fluoromethyl group, a trifluoromethyl group, amethoxymethyl group, a methoxyethyl group, and the like.

Examples of the aryl group include a phenyl group, a naphthyl group, andthe like, and the aryl group may have a substituent. Examples of thesubstituent include the above alkyl group, the above alkoxy group, theabove halogen atom, and an acyl group such as an acetyl group, apropionyl group, and the like, etc. and examples of the aryl groupsubstituted with the substituent include a 2-fluorophenyl group, a3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a3-chlorophenyl group, a 4-chlorophenyl group, a 2-bromophenyl group, a2-methylphenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a4-acetylphenyl group, and the like.

Examples of the cyclic ketone compound include cyclopropanone,cyclobutanone, 3-methylcyclobutanone, 3-phenylcyclobutanone,cyclopentanone, 2-methylcyclopentanone, 2-phenylcyclopentanone,cyclohexanone, 2-methylcyclohexanone, 2-phenylcyclohexanone,4-methylcyclohexanone, 4-phenylcyclohexanone, 4-chlorocyclohexaone,cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone,1,4-cyclohexanedione, adamantanone, and the like.

The amount of the metallized mesoporous silicate catalyst to be used inthe reaction of the ketone compound and hydrogen peroxide may be acatalytic amount relative to the ketone compound, and is usually 0.001part by weight or more relative to 1 part by weight of the ketonecompound. The upper limit is not particularly defined but, from theeconomical viewpoint, the amount is practically 1 part by weight or lessrelative to 1 part by weight of the ketone compound.

As hydrogen peroxide, an aqueous solution is usually used. Of course, asolution of hydrogen peroxide in an organic solvent may be used. Theconcentration of hydrogen peroxide in an aqueous hydrogen peroxidesolution or in a solution of hydrogen peroxide in an organic solvent isnot particularly limited, but in view of volume efficacy and safety, theconcentration is practically 1 to 60% by weight. As an aqueous hydrogenperoxide solution, usually, a commercially available aqueous hydrogenperoxide solution may be used as it is, or if necessary, by adjustingthe concentration thereof by dilution, concentration, and the like. As asolution of hydrogen peroxide in an organic solvent, for example, asolution prepared by means of extraction of an aqueous hydrogen peroxidesolution with an organic solvent, distillation of an aqueous hydrogenperoxide solution in the presence of an organic solvent, and the like,may be used.

The amount of hydrogen peroxide to be used is usually 0.4 mole or more,preferably 1 mole or more relative to 1 mole of the ketone compound. Theupper limit is not particularly defined but, when the amount is toolarge, it is liable to be economically disadvantageous. Then, the amountis practically 10 mole or less relative to 1 mole of a ketone compound.

The reaction of the ketone compound and hydrogen peroxide may be carriedout without a solvent, or may be carried out in water, in an organicsolvent, or in a mixture of water and an organic solvent. Examples ofthe organic solvent include an ether solvent such as diethyl ether,methyl tert-butyl ether, diglyme, or the like, a tertiary alcoholsolvent such as tert-butanol, or the like, a nitrile solvent such asacetonitrile, propionitrile, or the like, etc.

The reaction of the ketone compound and hydrogen peroxide is usuallycarried out by contacting and mixing the metallized mesoporous silicatecatalyst, the ketone compound and hydrogen peroxide, and the order ofmixing is not particularly limited.

The reaction temperature is usually −10 to 130° C., and the reaction isusually carried out at ordinary pressure, or may be carried out underreduced pressure or pressurized conditions.

As the reaction proceeds, a lactone compound is produced, and theprogress of the reaction can be confirmed by a conventional analyticalmeans such as gas chromatography, high performance liquidchromatography, thin layer chromatography, NMR, IR, and the like.

After completion of the reaction, the desired lactone compound can beisolated by subjecting the reaction mixture as it is, or, if necessary,after degrading remaining hydrogen peroxide with a reducing agent suchas sodium sulfite, and separating the metallized mesoporous silicate byfiltration, and the like, to concentration, crystallization and thelike. Further, by addition of water and/or a water-insoluble organicsolvent to the reaction mixture, if necessary, followed by extractionand concentration of the resulting organic layer, a lactone compound canbe isolated. The isolated lactone compound may be further purified by aconventional purification method such as distillation, columnchromatography, recrystallization, and the like.

The metallized mesoporous silicate catalyst or a solution of themetallized mesoporous silicate catalyst separated by filtration, liquidphase separation, and the like can be re-used as a catalyst in thereaction of a ketone compound and hydrogen oxide as it is, or, ifnecessary, after concentration, and the like.

Examples of the thus obtained lactone compound include β-propiolactone,γ-butyrolactone, β-methyl-γ-butyrolactone, β-phenyl-γ-butyrolactone,δ-valerolactone, ε-valerolactone, α-phenyl-δ-valerolactone,δ-phenyl-δ-valerolactone, ε-caprolactone, α-methyl-ε-caprolactone,ε-methyl-ε-caprolactone, α-phenyl-ε-caprolactone,ε-phenyl-ε-caprolactone, and the like.

Then, a process for producing an aromatic carboxylic acid ester of analcohol by reacting an aromatic aldehyde compound and the alcoholcompound will be illustrated.

The aromatic ring (which is represented by Ar in FIG. 1) of the aromaticaldehyde compound may be substituted with the same alkyl group, alkoxygroup, aryl group, and halogen atom as those defined with respect to theabove R₁ to R₄, and the like.

Examples of the alkyl group include straight, branched or cyclic alkylgroups such as a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group,a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-octyl group,an isooctyl group, a n-nonyl group, a n-decyl group, a cyclopentylgroup, a cyclohexyl group, and the like. The alkyl group may have asubstituent, and examples of the substituent include an alkoxy groupsuch as a methoxy group, an ethoxy group, a n-propoxy group, anisopropoxy group, a n-butoxy group, or the like, and a halogen atom suchas a fluorine atom, a chlorine atom, a bromine atom, or the like.Examples of the alkyl group having the substituent include achloromethyl group, a fluoromethyl group, a trifluoromethyl group, amethoxymethyl group, a methoxyethyl group, and the like.

Examples of the aryl group include a phenyl group, a naphthyl group, andthe like, and the aryl group may have a substituent. Examples of thesubstituent include the above alkyl group, the above alkoxy group, theabove halogen atom, an acyl group such as an acetyl group, a propionylgroup, or the like, etc. Examples of the aryl group substituted with thesubstituent include a 2-fluorophenyl group, a 3-fluorophenyl group, a4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a4-chlorophenyl group, a 2-bromophenyl group, a 2-methylphenyl group, a4-methylphenyl group, a 4-methoxyphenyl group, a 4-acetylphenyl group,and the like.

Examples of the aromatic aldehyde compound include benzaldehyde,2-fluorobenzaldehyde, 2-chlorobenzaldehyde, 2-bromobenzaldehyde,3-fluorobenzaldehyde, 3-chlorobenzaldehyde, 3-bromobenzaldehyde,4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 4-bromobenzaldehyde,2,4-difluorobenzaldehyde, 2,4-dichlorobenzaldehyde,3,5-difluorobenzaldehyde, 3-phenoxybenzaldehyde, 4-methylbenzaldehyde,3-trifluoromethylbenzaldehyde, 2-methoxybenzaldehyde,1-naphthylaldehyde, and the like.

Examples of the alcohol compound include the alcohol compoundrepresented by the formula (9): R₆OH [wherein R₆ represents a C₁₋₄primary or secondary alkyl group] in FIG. 1, and specific examplesinclude a primary alcohol compound and a secondary alcohol compoundhaving 1 to 4 carbon atoms such as methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol, and the like.

The amount of the alcohol compound to be used is usually 1 mole or morerelative to 1 mole of the olefin compound to be used, and its upperlimit is not particularly defined. For example, the alcohol compound maybe used in large excess relative to the olefin compound so as to alsoserve as a reaction solvent.

The amount of the metallized mesoporous silicate catalyst to be used inthe reaction of the aromatic aldehyde compound and hydrogen peroxidewhich is carried out in the presence of the alcohol compound may be acatalytic amount, and is usually 0.001 part by weight or more relativeto 1 part by weight of the aromatic aldehyde compound. Its upper limitis not particularly defined, but from the economical viewpoint, theamount is practically 1 part by weight or less relative to 1 part byweight of the aromatic aldehyde compound.

As hydrogen peroxide, an aqueous solution is usually used. Of course, asolution of hydrogen peroxide in an organic solvent may be used. Theconcentration of hydrogen peroxide in an aqueous hydrogen peroxidesolution or in a solution of hydrogen peroxide in an organic solvent isnot particularly limited, but in view of volume efficacy and safety, theconcentration is practically 1 to 60% by weight. As an aqueous hydrogenperoxide solution, usually, a commercially available aqueous hydrogenperoxide solution may be used as it is, or, if necessary, by adjustingthe concentration thereof by dilution, concentration, and the like. As asolution of hydrogen peroxide in an organic solvent, for example, asolution prepared by extracting an aqueous hydrogen peroxide solutionwith an organic solvent, or distilling an aqueous hydrogen peroxidesolution in the presence of an organic solvent, may be used.

The amount of hydrogen peroxide to be used is usually 0.4 mole or more,preferably 1 mole or more relative to 1 mole of the aromatic aldehydecompound. Its upper limit is not particularly defined, but when theamount rises too much, it is liable to be economically disadvantageous.Then, the amount is practically 10 moles or less.

The reaction of the aromatic aldehyde compound and hydrogen peroxidewhich is carried out in the presence of the alcohol compound may becarried out by using the alcohol compound as a solvent, as describedabove, or may be carried out in water, in an organic solvent, or in amixture of water and an organic solvent. Examples of the organic solventinclude an ether solvent such as diethyl ether, methyl tert-butyl ether,diglyme, or the like, a nitrile solvent such as acetonitrile,propionitrile, or the like, etc.

The reaction of the aromatic aldehyde compound and hydrogen peroxidewhich is carried out in the presence of the alcohol compound is usuallycarried out by contacting and mixing the metallized mesoporous silicatecatalyst, the aromatic aldehyde compound, the alcohol compound andhydrogen peroxide, and the order of mixing is not particularly limited.

The reaction temperature is usually −10 to 130° C., and the reaction isusually carried out at ordinary pressure, but may be carried out underreduced pressure or pressurized conditions.

As the reaction proceeds, the aromatic ester compound is produced, andthe progress of the reaction can be confirmed by a conventionalanalytical means such as gas chromatography, high performance liquidchromatography, thin layer chromatography, NMR, IR, and the like.

After completion of the reaction, the desired aromatic ester compoundcan be isolated by subjecting the reaction mixture as it is, or ifnecessary, after degrading remaining hydrogen peroxide with a reducingagent such as sodium sulfite, and separating the metallized mesoporoussilicate catalyst by filtration, or the like, to concentration,crystallization, and the like. Alternatively, the aromatic estercompound can be isolated by, extracting the reaction mixture, ifnecessary, by adding water and/or a water-insoluble organic solventthereto, and concentrating the resulting organic layer. The isolatedaromatic ester compound may be further purified by a conventionalpurification method such as distillation, column chromatography,recrystallization, and the like.

The metallized mesoporous silicate catalyst, or a solution containingthe metallized mesoporous silicate catalyst separated by filtration,liquid phase separation, and the like, may be re-used as a catalyst forthe reaction of the aromatic aldehyde compound and hydrogen peroxidewhich is carried out in the presence of the alcohol compound, as it is,or if necessary, after concentration, and the like.

Examples of the aromatic ester compound thus obtained include methylbenzoate, ethyl 2-fluorobenzoate, propyl 2-chlorobenzoate, butyl2-bromobenzoate, methyl 3-fluorobenzoate, ethyl 3-chlorobenzoate, methyl3-bromobenzoate, ethyl 4-fluorobenzoate, methyl 4-chlorobenzoate, methyl4-bromobenzoate, methyl 2,4-difluorobenzoate, methyl2,4-dichlorobenzoate, methyl 3,5-difluorobenzoate, methyl3-phenoxybenzoate, methyl 4-benzoate, methyl 3-trifluoromethylbenzoate,methyl 2-methoxybenzoate, 1-carbomethoxynaphthalene, and the like.

EXAMPLES

The following Examples further illustrate the present invention indetail, but the present invention is not limited by these Examples. Theanalysis was carried out by gas chromatography (hereinafter, abbreviatedas GC) and high performance liquid chromatography (hereinafter, referredto as LC). Respective analytical conditions are as follows:

<GC Analytical Conditions>

Column: DB-1 (φ0.25 μm×30 m, membrane thickness 1.0 μm)

Carrier gas: helium (flow rate: 1 m/min)

Split ratio: 1/10, Sample injection amount: 1 μL

Column temperature: 100° C. (0 min)→180° C. (temperature raising rate:2° C./min, retention time at 180° C.: 0 min)→300° C. (temperatureraising rate: 10° C./min, retention time at 300° C.: 15 min)

Injection inlet temperature: 200° C., detector temperature: 250° C.

<LC Analytical Conditions>

Column: SUMIPAX ODS A-212 (5 μm, φ6 mm×15 cm)

Mobile phase: A solution, 0.1% by volume aqueous trifluoroacetic acidsolution

B solution, 0.1% by volume trifluoroacetic acid/acetonitrile solution

The composition was linearly changed from A solution/B solution=90/10(volume ratio) to A solution/B solution=10/90 (volume ratio) for 40minutes, and was retained at the composition ratio of A solution/Bsolution=10/90 (volume ratio) for 20 minutes.

Flow rate: 1.0 mL/min, sample injection amount: 10 μL, detectionwavelength: 220 nm

Example 1

<Preparation of Tungsten-Containing Mesoporous Silicate usingAlkylamine>

To a 500 mL flask equipped with an induction stirrer were added 1 g of atungsten metal powder and 5 g of ion-exchanged water, an innertemperature was raised to 40° C., 3 g of a 60% by weight aqueoushydrogen peroxide solution was added dropwise thereto over 30 minutes,and the mixture was maintained at the same temperature for 1 hour toobtain a tungsten oxide-containing solution. To the tungstenoxide-containing solution were added 100 g of ion-exchanged water and 80g of ethanol, and then 10 g of dodecylamine was added dropwise theretoat an inner temperature of 40° C. over 30 minutes. Then, the mixture wascooled to an inner temperature of 25° C., and 41.6 g oftetraethoxysilane was added dropwise thereto over 30 minutes. Whenstirring was continued at an inner temperature of 25° C., crystalsprecipitated in about 30 minutes to form slurry, and this was furtherstirred and maintained at the same temperature for 24 hours. From theresulting slurry, crystals were collected by filtration, washed with 100g of ion-exchanged water twice, and dried at 110° C. for 6 hours. Thewhite crystals were calcined at 550° C. for 6 hours to obtain 15.0 g ofa white solid.

XRD spectrum: A broad peak having an apex at a d value of 3.79 Å isobserved. A peak assignable to tungsten oxide is not observed.

IR spectrum of the resulting solid (KBr) ν_(max): 3471, 1636, 1080, 972,804 cm⁻¹

Elemental analysis value: W, 2.43%; Si, 35.6%

Specific surface area (nitrogen absorption method): 696 m²/g

Micropore diameter (nitrogen absorption method): 32 Å

Example 2

<Preparation of Tungsten-Containing Mesoporous Silicate using QuaternaryAmmonium Salt>

To a 500 mL flask equipped with an induction stirrer were added 5 g of atungsten metal powder and 25 g of ion-exchanged water, an innertemperature was raised to 40° C., 15 g of a 60% by weight aqueoushydrogen peroxide solution was added dropwise thereto over 30 minutes,and the mixture was maintained at the same temperature for 1 hour toobtain a tungsten oxide-containing solution. To the tungstenoxide-containing solution were added 75 g of ion-exchanged water and 80g of ethanol, and then 8 g of tetrabutylammonium hydroxide salt wasadded dropwise thereto at an inner temperature of 40° C. over 30minutes. Then, the mixture was cooled to an inner temperature of 25° C.,and 41.6 g of tetraethoxysilane was added dropwise thereto over 30minutes. When stirring was continued at an inner temperature of 25° C.,crystals were precipitated in about 30 minutes to form slurry, and thiswas stirred and maintained at the same temperature for 24 hours. Fromthe resulting slurry, crystals were collected by filtration, washed with100 g of ion-exchanged water twice, and dried at 130° C. for 24 hours toobtain 33.0 g of white crystals. 16.0 g of the white crystals werecalcined at 550° C. for 6 hours to obtain 7.8 g of a white solid.

XRD spectrum: A spectrum of a mixture of a broad peak having an apex ata d value of 3.79 Å, and a sharp peak assignable to tungsten oxide isobserved.

IR spectrum of the resulting solid (KBr) ν_(max): 3484, 1642, 1081, 950,813, 783 cm⁻¹

Elemental analysis value: W, 23.9%; Si, 28.4%

Specific surface area (nitrogen absorption method): 514 m²/g

Micropore diameter (nitrogen absorption method): 32 Å

Example 3

<Preparation of Tungsten-Containing Mesoporous Silicate using QuaternaryAmmonium Salt>

To a 500 mL flask equipped with an induction stirrer were added 5 g of atungsten metal powder and 25 g of ion-exchanged water, an innertemperature was raised to 40° C., 15 g of a 60% by weight aqueoushydrogen peroxide solution was added dropwise over 30 minutes thereto,and the mixture was maintained at the same temperature for 2 hours toobtain a tungsten oxide-containing solution. To the tungstenoxide-containing solution were added 75 g of ion-exchanged water and 80g of ethanol, 41.6 g of tetraethoxysilane was charged therein at aninner temperature of 40° C. over 10 minutes, and 20 g of a 40% aqueoustetrabutylammonium hydroxide solution was added dropwise thereto over 10minutes. Then, the mixture was cooled to an inner temperature of 25° C.and, when stirring was continued, crystals were precipitated in about 30minutes to form slurry, and the mixture was stirred and maintained atthe same temperature for 24 hours. From the resulting slurry, crystalswere collected by filration, washed with 100 g of ion-exchanged watertwice, and dried at 130° C. for 24 hours to obtain 38.0 g of whitecrystals. The white crystals were calcined at 550° C. for 6 hours toobtain 16.5 g of a white solid.

XRD spectrum: A broad peak having an apex at a d value of 3.77 Å isobserved. A sharp peak assignable to tungsten oxide is not observed.

IR spectrum of the resulting solid (KBr) υ_(max): 3478, 1638, 1078, 960,806, 557 cm⁻¹

Elemental analysis value: W, 9.8%; Si, 39.5%

Specific surface area (nitrogen absorption method): 543 m²/g

Micropore diameter (nitrogen absorption method): 16 Å

Example 4

<Preparation of Tungsten-Containing Mesoporous Silicate using QuaternaryAmmonium Salt>

To a 500 mL flask equipped with an induction stirrer were added 5 g of atungsten metal powder and 25 g of ion-exchanged water, an innertemperature was raised to 40° C., 15 g of a 60% by weight aqueoushydrogen peroxide solution was added dropwise thereto over 30 minutes,and the mixture was maintained at the same temperature for 2 hours toobtain a tungsten oxide-containing solution. To the tungstenoxide-containing solution were added 75 g of ion-exchanged water and 80g of ethanol, 41.6 g of tetraethoxysilane was charged therein at aninner temperature of 40° C. over 10 minutes, and 40 g of a 10%tetrapropylammonium hydroxide solution was added dropwise thereto over10 minutes. Then, the mixture was cooled to an inner temperature of 25°C. and, when stirring was continued, crystals were precipitated in about30 minutes to form slurry, and the mixture was stirred and maintained atthe same temperature for 24 hours. From the resulting slurry solution,crystals were collected by filtration, washed with 100 g ofion-exchanged water twice, and dried at 130° C. for 24 hours to obtain38.0 g of white crystals. The white crystals were calcined at 550° C.for 6 hours to obtain 17.3 g of a white solid.

XRD spectrum: A broad peak having an apex at a d value of 3.76 Å isobserved. A sharp peak assignable to tungsten oxide is slightlyobserved.

IR spectrum of the resulting solid (KBr) φ_(max): 3480, 1638, 1078, 956,800 cm⁻¹

Elemental analysis value: W, 11.0%; Si, 31.4%

Specific surface area (nitrogen absorption method): 573 m²/g

Micropore diameter (nitrogen absorption method): 22 Å

Comparative Example 1

<Preparation of Tungsten-Containing Mesoporous Silicate using QuaternaryAmmonium Salt>

According to the same manner as that of Example 4, 15.0 g of a whitesolid was obtained except that 6.8 g of tungstic acid was used in placeof 5 g of the tungsten metal powder in Example 4.

XRD spectrum: A broad peak having an apex at a d value of 3.89 Å isobserved. A sharp peak assignable to tungsten oxide is slightlyobserved.

IR spectrum of the resulting solid (KBr) υ_(max): 3480, 1638, 1080, 952,794 cm⁻¹

Elemental analysis value: W, 19.6%; Si, 30.9%

Specific surface area (nitrogen absorption method): 267 m²/g

Micropore diameter (nitrogen absorption method): 23 Å

Example 5

<Preparation of Molybdenum-Containing Mesoporous Silicate usingAlkylamine>

To a 500 mL flask equipped with an induction stirrer were added 2 g of amolybdenum metal powder and 25 g of ion-exchanged water, an innertemperature was raised to 40° C., 15 g of a 60% by weight aqueoushydrogen peroxide solution was added dropwise thereto over 1 hour, andthe mixture was maintained at the same temperature for 1 hour to obtaina molybdenum oxide-containing solution. To the molybdenumoxide-containing solution were added 75 g of ion-exchanged water and 80g of ethanol, 41.6 g of tetraethoxysilane was added thereto at an innertemperature of 40° C. over 10 minutes, and then 10 g of dodecyl aminewas added dropwise over thereto 10 minutes. Crystals were precipitatedimmediately to form slurry and, then, the mixture was cooled to an innertemperature of 25° C., and stirred and maintained at the sametemperature for 24 hours. From the resulting slurry, crystals werecollected by filtration, washed with 100 g of ion-exchanged water twice,and dried at 110° C. for 6 hours. The white crystals were calcined at550° C. for 6 hours to obtain 15.5 g of a white solid.

XRD spectrum: A mixed spectrum of a broad peak having an apex at a dvalue of 3.8 Å and a sharp peak assignable to molybdenum oxide isobserved.

IR spectrum of resulting solid (KBr) υ_(max): 3470, 1640, 1090, 956,915, 802 cm⁻¹

Elemental analysis value: Mo, 13.9%; Si, 32.4%

Specific surface area (nitrogen absorption method): 171 m²/g

Micropore diameter (nitrogen absorption method): 73 Å

Example 6

<Preparation of Molybdenum Containing Mesoporous Silicate usingQuaternary Ammonium Salt>

To a 500 mL flask equipped with an induction stirrer were added 2.5 g ofa molybdenum metal powder and 25 g of ion-exchanged water, an innertemperature was raised to 40° C., 15 g of a 60% by weight aqueoushydrogen peroxide solution was added dropwise thereto over 1 hour, andthe mixture was maintained at the same temperature for 1 hour to obtaina molybdenum oxide-containing solution. To the molybdenumoxide-containing solution were added 75 g of ion-exchanged water and 80g of ethanol, 41.6 g of tetraethoxysilane was added thereto at an innertemperature of 40° C. over 10 minutes, and then 20 g of a 40% aqueoustetrabutylammonium hydroxide solution was added dropwise thereto over 10minutes. Crystals were precipitated in about 15 minutes to form slurry,200 g of ion-exchanged water was further added thereto, and the mixturewas cooled to an inner temperature of 25° C., and stirred and maintainedat the same temperature for 24 hours. From the resulting slurry,crystals were collected by filtration, washed with 100 g ofion-exchanged water twice, and dried at 110° C. for 6 hours. The whitecrystals were calcined at 550° C. for 6 hours to obtain 15.9 g of awhite solid.

XRD spectrum: A broad peak having an apex at a d value of 3.79 Å isobserved. A sharp peak assignable to molybdenum oxide is not observed.

IR spectrum of the resulting solid (KBr) υ_(max): 3470, 1640, 1080, 956,913, 796 cm⁻¹

Elemental analysis value: Mo, 5.22%; Si, 37.0%

Specific surface area (nitrogen absorption method): 649 m²/g

Micropore diameter (nitrogen absorption method): 22 Å

Example 7

<Preparation of Vanadium-Containing Mesoporous Silicate using QuaternaryAmmonium Salt>

To a 500 mL flask equipped with an induction stirrer were added 1.3 g ofa vanadium metal powder and 25 g of ion-exchanged water, an innertemperature was raised to 40° C., 15 g of a 30% by weight aqueoushydrogen peroxide solution was added dropwise thereto over 30 minutes,and the mixture was maintained at the same temperature for 1 hour toobtain a vanadium oxide-containing solution. To the vanadiumoxide-containing solution were added 75 g of ion-exchanged water and 80g of ethanol, 41.6 g of tetraethoxysilane was added thereto at an innertemperature of 40° C. for 10 minutes, and then 40 g of a 40% aqueoustetra-n-propylamine solution was added dropwise thereto over 10 minutes.Then, the mixture was cooled to an inner temperature of 25° C., whenstirring was continued, crystals were precipitated in about 30 minutesto form slurry, and the mixture was stirred and maintained at the sametemperature for 24 hours. From the resulting slurry, crystals werecollected by filtration, washed with 100 g of ion-exchanged water twice,and dried at 130° C. for 8 hours. The white crystals were calcined at550° C. for 6 hours to obtain 16.0 g of a brown solid.

XRD spectrum: A broad peak having an apex at a d value of 3.85 Å isobserved.

IR spectrum of resulting solid (KBr) υ_(max): 1050, 956, 794, 629 cm⁻¹

Elemental analysis value: V, 5.56%; Si, 36.1%

Example 8

To a 50 mL flask equipped with a magnetic stirrer and a reflux condenserwere added 800 mg of the tungsten-containing mesoporous silicateprepared in Example 1, 800 mg of a 60% by weight aqueous hydrogenperoxide solution, 2 g of tert-butanol and 400 mg of 1-heptene, and themixture was stirred and maintained at an inner temperature of 40° C. for16 hours to react these materials. To the resulting reaction mixture wasadded 5 g of methyl tert-butyl ether, and the mixture was stirred, andthen allowed to stand. The supernatant organic layer was analyzed by LC,and it was found that 2-hydroperoxy-l-hydroxyheptane and1-hydroperoxy-2-hydroxyheptane were produced. When the organic layer wasanalyzed by GC, 2-hydroperoxy-1-hydroxyheptane and1-hydroperoxy-2-hydroxyheptane were thermally decomposed at an injectioninlet, and detected as 1-hexanal. Then, the yield of 1-hexanal wasdetermined by GC analysis (internal standard method), and this wasregarded as the yield of 2-hydroperoxy-1-hydroxyheptane and1-hydroperoxy-2-hydroxyheptane. Yield: 22%. The recovery of 1-hexene was67%.

Example 9

To a 50 mL flask equipped with a magnetic stirrer and a refluxingcondensing tube were added 300 mg of the tungsten-containing mesoporoussilicate prepared in Example 2, 760 mg of 60% by weight aqueous hydrogenperoxide solution, 3 g of tert-butanol and 500 mg of 1-octene, and themixture was stirred and maintained at an inner temperature of 50° C. for16 hours to react these materials. To the resulting reaction mixture wasadded 5 g of methyl tert-butyl ether, and the mixture was stirred, andallowed to stand. The supernatant organic layer was analyzed by LC, andit was found that 2-hydroperoxy-1-hydroxyoctane and1-hydroperoxy-2-hydroxyoctane were produced. When the organic layer wasanalyzed by GC, 2-hydroperoxy-1-hydroxyoctane and1-hydroperoxy-2-hydroxyoctane were thermally decomposed at an injectioninlet, and detected as 1-heptanal. Then, the yield of 1-heptanal wasdetermined by GC analysis (internal standard method), and this wasregarded as the yield of 2-hydroperoxy-1-hydroxyoctane and1-hydroperoxy-2-hydroxyoctane. Yield: 42%

Example 10

To a 50 mL flask equipped with a magnetic stirrer and a refluxingcondensing tube were added 200 mg of the tungsten-containing mesoporoussilicate synthesized in Example 1, 285 mg of 60% by weight aqueoushydrogen peroxide solution, 24 g of ethanol and 410 mg of cyclohexene,and the mixture was stirred and maintained at an inner temperature of80° C. for 6 hours to react these materials. The resulting reactionmixture was analyzed by GC (internal standard method), and the yield ofthe products was determined.

Yield of 2-ethoxycyclohexanol: 50%

Yield of 1,2-cyclohexanediol: 5%

The recovery of the starting material, cyclohexene, was 40%.

Example 11

To 50 mL flask equipped with a magnetic stirrer and a refluxingcondensing tube were added 200 mg of the tungsten-containing mesoporoussilicate synthesized in Example 3, 285 mg of a 60% by weight aqueoushydrogen peroxide solution, 24 g of ethanol and 410 mg of cyclohexene,and the mixture was stirred and maintained at an inner temperature of80° C. for 6 hours to react these materials. The resulting reactionmixture was analyzed by GC (internal standard method), and the yield ofthe products was determined.

Yield of 2-ethoxycyclohexanol: 61%

Yield of 1,2-cyclohexanediol: 1.7%

The recovery of the starting material, cyclohexene, was 35%.

Example 12

To a 100 mL flask equipped with a magnetic stirrer and a refluxcondenser were added 300 mg of the tungsten-containing mesoporoussilicate synthesized in Example 2, 10 g of methanol and 3.08 g ofcyclohexene, and an inner temperature was raised to 65° C. A mixedsolution containing 4.3 g of a 30% by weight aqueous hydrogen peroxidesolution and 10 g of methanol was added dropwise thereto with stirringover 3 hours, and the mixture was maintained for 1 hour. The resultingreaction solution was analyzed by GC (internal standard method), and theyield of the products was determined.

Yield of 2-methoxycyclohexanol: 33%

1,2-Cyclohexanediol was not detected.

The recovery of the starting material, cyclohexene, was 65%.

Example 13

According to a similar manner as that of Example 12, the yield of theproducts was determined except that 300 mg of the tungsten-containingmesoporous silicate synthesized in Example 3 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 12.

Yield of 2-methoxycyclohexanol: 42.1%

1,2-Cyclohexanediol was not detected.

The recovery of the starting material, cyclohexene, was 55%.

Example 14

According to a similar manner as that of Example 12, the yield of theproducts was determined except that 300 mg of the tungsten-containingmesoporous silicate synthesized in Example 4 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 12.

Yield of 2-methoxycyclohexanol: 64%

Yield of 1,2-cyclohexanediol: 1%

The recovery of the starting material, cyclohexene, was 33%.

Comparative Example 2

According a similar manner as that of Example 12, the yield of theproducts was determined except that 300 mg of the tungsten-containingmesoporous silicate synthesized in Comparative Example 1 was used inplace of the tungsten-containing mesoporous silicate synthesized inExample 2, in Example 12.

Yield of 2-methoxycyclohexanol: 35%

Yield of 1,2-cyclohexanediol: 8%

The recovery of the starting material, cyclohexene, was 53%.

Example 15

According to a similar manner as that of Example 12, the yield of theproducts was determined except that 300 mg of the molybdenum-containingmesoporous silicate synthesized in Example 5 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 12.

Yield of 2-methoxycyclohexanol: 55.4%

Yield of 1,2-cyclohexanediol: 1%

The recovery of the starting material, cyclohexene, was 42%.

Example 16

According to a similar manner as that of Example 12, the yield of theproducts was determined except that 300 mg of the molybdenum-containingmesoporous silicate synthesized in Example 6 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 12.

Yield of 2-methoxycyclohexanol: 28.5%

1,2-Cyclohexanediol was not detected.

The recovery of the starting material, cyclohexene, was 70%.

Example 17

A 100 mL flask equipped with a magnetic stirrer and a refluxingcondensing tube was charged with 50 mg of the tungsten-containingmesoporous silicate synthesized in Example 2, 5 g of methanol and 500 mgof benzaldehyde, and an inner temperature was raised to 65° C. A mixedsolution containing 1.6 g of a 30% by weight aqueous hydrogen peroxidesolution and 5 g of methanol was added dropwise with stirring theretoover 3 hours, and the mixture was maintained for 1 hour. The resultingreaction mixture was analyzed by GC (internal standard method), and theyield of the products was determined.

Yield of benzoic acid methyl ester: 71%

The recovery of the starting material, benzaldehyde, was 25%.

Example 18

According to a similar manner as that of Example 17, the yield of theproducts was determined except that 50 mg of the tungsten-containingmesoporous silicate synthesized in Example 4 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 17.

Yield of benzoic acid methyl ester: 75%

The recovery of the starting material, benzaldehyde, was 20%.

Example 19

According to a similar manner as that of Example 17, the yield of theproducts was determined except that 50 mg of the molybdenum-containingmesoporous silicate synthesized in Example 5 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 17.

Yield of benzoic acid methyl ester: 75%

The recovery of the starting material, benzaldehyde, was 20%.

Example 20

According to a similar manner as that of Example 17, the yield of theproducts was determined except that 50 mg of the vanadium-containingmesoporous silicate synthesized in Example 7 was used in place of thetungsten-containing mesoporous silicate synthesized in Example 2, inExample 17.

Yield of benzoic acid methyl ester: 95%

The recovery of the starting material, benzaldehyde, was 2%.

Example 21

To a 50 mL flask equipped with a magnetic stirrer and a refluxingcondensing tube were added 100 mg of the tungsten-containing mesoporoussilicate synthesized in Example 2, 340 mg of a 60% by weight aqueoushydrogen peroxide solution, 5 g of acetonitrile and 500 mg ofcyclopentanone, and the mixture was stirred and maintained at an innertemperature of 80° C. for 4 hours to react these materials. Theresulting reaction mixture was analyzed by GC (internal standardmethod), the yield of the products was determined.

Yield of δ-valerolactone: 22.1%.

The recovery of the starting material, cyclopentanone, was 77%.

INDUSTRIAL APPLICABILITY

According to the present invention, metallized mesoporous silicateobtained by reacting a silicon compound, and metal peroxide obtained byreacting any one selected from easily available tungsten metal,molybdenum metal, vanadium metal, and the aforementioned metal compoundthereof, with hydrogen peroxide, in the presence of alkylamine orquaternary ammonium salt, has oxidation reaction catalytic activity and,at the same time, alkylation reaction catalytic activity, and is anadvantageous catalyst from an industrially point of view. For example,by reacting hydrogen peroxide which is an inexpensive oxidizing agent,with an organic compound such as an olefin compound and a ketonecompound in the presence of the metallized mesoporous silicate catalystof the present invention, oxygen-containing organic compounds such as aβ-hydroxyhydroperoxide compound, a diol compound, a lactone compound, a2-alkoxyalcohol compound, and an aromatic ester compound can beproduced.

1. A metallized mesoporous silicate containing at least one memberselected from tungsten, molybdenum and vanadium, which is obtained by:(i) a step of reacting: (a) a metal peroxide obtained by reacting atleast one metal or metal compound selected from the group consisting ofthe following 1) to 3) groups with aqueous hydrogen peroxidesolution, 1) tungsten metal, 2) molybdenum metal, 3) vanadium metal, ora solution thereof, with (b) a silicon compound, in the presence of analkylamine or a quaternary ammonium salt, and (ii) a step of separatingthe resultant reaction product from the reaction mixture.
 2. Themetallized mesoporous silicate according to claim 1, wherein the siliconcompound is a tetraalkoxysilane.
 3. The metallized mesoporous silicateaccording to claim 1, wherein the alkylamine is a primary amine.
 4. Themetallized mesoporous silicate according to claim 1, wherein thequaternary ammonium salt is a tetraalkylammonium hydroxide.
 5. A processfor producing a diol or β-hydroxyhydroperoxide, which comprises reactinghydrogen peroxide and an olefin in the presence of the metallizedmesoporous silicate according to claim
 1. 6. A process for producing a2-alkoxyalcohol, which comprises reacting hydrogen peroxide, an olefin,and an alcohol in the presence of the metallized mesoporous silicateaccording to claim
 1. 7. A process for producing an ester compound,which comprises reacting hydrogen peroxide and a ketone in the presenceof the metallized mesoporous silicate according to claim
 1. 8. Theprocess according to claim 7, wherein the ketone is a cyclic ketone, anda Baeyer-Villiger reaction product is a cyclic lactone.
 9. A process forproducing an aromatic carboxylic acid ester of an alcohol, whichcomprises reacting hydrogen peroxide, an aromatic aldehyde and thealcohol in the presence of the metallized mesoporous silicate accordingto claim
 1. 10. A process for producing a metallized mesoporous silicatecontaining at least one member selected from tungsten, molybdenum andvanadium, which comprises: (i) a step of reacting: (a) a metal peroxideobtained by reacting at least one metal or metal compound selected fromthe group consisting of the following 1) to 6) groups with an aqueoushydrogen peroxide solution, 1) tungsten metal, 2) molybdenum metal, 3)vanadium metal, 4) a tungsten compound composed of 4a) tungsten and 4b)at least one element selected from the group consisting of Group 13,Group 14, Group 15 and Group 16 elements except for oxygen, 5) amolybdenum compound composed of 5a) molybdenum and 5b) at least oneelement selected from the group consisting of Group 13, Group 14, Group15 and Group 16 elements except for oxygen, and 6) a vanadium compoundcomposed of 6a) vanadium and 6b) at least one element selected from thegroup consisting of Group 13, Group 14, Group 15 and Group 16 elementsexcept for oxygen, or a salt thereof, with (b) a silicon compound, inthe presence of an alkylamine or a quaternary ammonium salt, and (ii) astep of separating the resultant reaction product from the reactionmixture.
 11. The process for producing metallized mesoporous silicateaccording to claim 10, wherein the silicon compound is atetraalkoxysilane.
 12. The process for producing metallized mesoporoussilicate according to claim 10, wherein the alkylamine is a primaryamine.
 13. The process for producing metallized mesoporous silicateaccording to claim 10, wherein the quaternary ammonium salt is atetraalkylammonium hydroxide.